ES2620115T3 - Copper-nickel alloy electroplating bath and plating method - Google Patents
Copper-nickel alloy electroplating bath and plating method Download PDFInfo
- Publication number
- ES2620115T3 ES2620115T3 ES13779037.4T ES13779037T ES2620115T3 ES 2620115 T3 ES2620115 T3 ES 2620115T3 ES 13779037 T ES13779037 T ES 13779037T ES 2620115 T3 ES2620115 T3 ES 2620115T3
- Authority
- ES
- Spain
- Prior art keywords
- copper
- salts
- group
- nickel
- nickel alloy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 48
- 239000000956 alloy Substances 0.000 title claims abstract description 48
- 229910000570 Cupronickel Inorganic materials 0.000 title claims abstract description 34
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000009713 electroplating Methods 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims description 11
- 238000007747 plating Methods 0.000 title description 63
- 150000003839 salts Chemical class 0.000 claims abstract description 63
- 150000001875 compounds Chemical class 0.000 claims abstract description 29
- 229910052751 metal Inorganic materials 0.000 claims abstract description 27
- 239000002184 metal Substances 0.000 claims abstract description 27
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000001413 amino acids Chemical class 0.000 claims abstract description 14
- 239000008139 complexing agent Substances 0.000 claims abstract description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011593 sulfur Substances 0.000 claims abstract description 12
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 12
- 150000001879 copper Chemical class 0.000 claims abstract description 10
- 150000002019 disulfides Chemical class 0.000 claims abstract description 10
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical class NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910001502 inorganic halide Inorganic materials 0.000 claims abstract description 9
- 229940124530 sulfonamide Drugs 0.000 claims abstract description 9
- 150000003456 sulfonamides Chemical class 0.000 claims abstract description 9
- 150000003460 sulfonic acids Chemical class 0.000 claims abstract description 9
- 229910052920 inorganic sulfate Inorganic materials 0.000 claims abstract description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 47
- 239000010949 copper Substances 0.000 claims description 47
- 229910052802 copper Inorganic materials 0.000 claims description 43
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 42
- 239000000203 mixture Substances 0.000 claims description 35
- 229910052759 nickel Inorganic materials 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 23
- 238000000576 coating method Methods 0.000 claims description 22
- 239000011248 coating agent Substances 0.000 claims description 19
- -1 disulfide compound Chemical class 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 12
- 229910052709 silver Inorganic materials 0.000 claims description 12
- 239000004332 silver Substances 0.000 claims description 12
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 claims description 9
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 8
- 150000007513 acids Chemical class 0.000 claims description 7
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 235000019204 saccharin Nutrition 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 125000003700 epoxy group Chemical group 0.000 claims description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 4
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 229940081974 saccharin Drugs 0.000 claims description 4
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 159000000003 magnesium salts Chemical class 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 239000004033 plastic Substances 0.000 claims description 3
- 229920003023 plastic Polymers 0.000 claims description 3
- 159000000001 potassium salts Chemical class 0.000 claims description 3
- 159000000000 sodium salts Chemical class 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 229910006069 SO3H Inorganic materials 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- 241000933336 Ziziphus rignonii Species 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 150000003842 bromide salts Chemical class 0.000 claims description 2
- 150000003841 chloride salts Chemical class 0.000 claims description 2
- 238000006482 condensation reaction Methods 0.000 claims description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 150000002763 monocarboxylic acids Chemical class 0.000 claims description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 2
- 235000011151 potassium sulphates Nutrition 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims description 2
- 229920003169 water-soluble polymer Polymers 0.000 claims description 2
- 238000005246 galvanizing Methods 0.000 claims 2
- 238000000151 deposition Methods 0.000 claims 1
- 150000004694 iodide salts Chemical class 0.000 claims 1
- 150000002815 nickel Chemical class 0.000 abstract description 7
- 230000000052 comparative effect Effects 0.000 description 22
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical class CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000013019 agitation Methods 0.000 description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 11
- 235000001014 amino acid Nutrition 0.000 description 10
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- 230000008021 deposition Effects 0.000 description 9
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 8
- RYZCLUQMCYZBJQ-UHFFFAOYSA-H lead(2+);dicarbonate;dihydroxide Chemical compound [OH-].[OH-].[Pb+2].[Pb+2].[Pb+2].[O-]C([O-])=O.[O-]C([O-])=O RYZCLUQMCYZBJQ-UHFFFAOYSA-H 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- ALKZAGKDWUSJED-UHFFFAOYSA-N dinuclear copper ion Chemical compound [Cu].[Cu] ALKZAGKDWUSJED-UHFFFAOYSA-N 0.000 description 5
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 4
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 4
- 239000000174 gluconic acid Substances 0.000 description 4
- 235000012208 gluconic acid Nutrition 0.000 description 4
- 235000011187 glycerol Nutrition 0.000 description 4
- 229940098779 methanesulfonic acid Drugs 0.000 description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- 241000894007 species Species 0.000 description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 3
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 239000008199 coating composition Substances 0.000 description 3
- ZQLBQWDYEGOYSW-UHFFFAOYSA-L copper;disulfamate Chemical class [Cu+2].NS([O-])(=O)=O.NS([O-])(=O)=O ZQLBQWDYEGOYSW-UHFFFAOYSA-L 0.000 description 3
- YGSZNSDQUQYJCY-UHFFFAOYSA-L disodium;naphthalene-1,5-disulfonate Chemical compound [Na+].[Na+].C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1S([O-])(=O)=O YGSZNSDQUQYJCY-UHFFFAOYSA-L 0.000 description 3
- 239000001630 malic acid Substances 0.000 description 3
- 235000011090 malic acid Nutrition 0.000 description 3
- CXIHYTLHIDQMGN-UHFFFAOYSA-L methanesulfonate;nickel(2+) Chemical compound [Ni+2].CS([O-])(=O)=O.CS([O-])(=O)=O CXIHYTLHIDQMGN-UHFFFAOYSA-L 0.000 description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 3
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 description 3
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 3
- 239000003002 pH adjusting agent Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 229940005657 pyrophosphoric acid Drugs 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 2
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 2
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 2
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 description 2
- ZVRQBAIVGPOQIN-UHFFFAOYSA-N NC(CCSSCCC(N)N)N Chemical compound NC(CCSSCCC(N)N)N ZVRQBAIVGPOQIN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910021538 borax Inorganic materials 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 2
- SDFNZYMSEOUVIF-UHFFFAOYSA-N copper;methanesulfonic acid Chemical compound [Cu].CS(O)(=O)=O SDFNZYMSEOUVIF-UHFFFAOYSA-N 0.000 description 2
- 235000011180 diphosphates Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000013922 glutamic acid Nutrition 0.000 description 2
- 239000004220 glutamic acid Substances 0.000 description 2
- 229930182817 methionine Natural products 0.000 description 2
- 229940078494 nickel acetate Drugs 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 229940048084 pyrophosphate Drugs 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000001509 sodium citrate Substances 0.000 description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 2
- 235000010339 sodium tetraborate Nutrition 0.000 description 2
- FMYOMWCQJXWGEN-UHFFFAOYSA-M sodium;2,3,4,5,6,7-hexahydroxyheptanoate Chemical compound [Na+].OCC(O)C(O)C(O)C(O)C(O)C([O-])=O FMYOMWCQJXWGEN-UHFFFAOYSA-M 0.000 description 2
- NJZLKINMWXQCHI-UHFFFAOYSA-N sodium;3-(3-sulfopropyldisulfanyl)propane-1-sulfonic acid Chemical compound [Na].[Na].OS(=O)(=O)CCCSSCCCS(O)(=O)=O NJZLKINMWXQCHI-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- 238000004876 x-ray fluorescence Methods 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- HZVFIGCZZJJEEF-UHFFFAOYSA-N 2-(2,2-diaminoethyldisulfanyl)ethane-1,1-diamine Chemical compound NC(N)CSSCC(N)N HZVFIGCZZJJEEF-UHFFFAOYSA-N 0.000 description 1
- APTMUIAOGSSQEM-UHFFFAOYSA-N 2-(2,2-dihydroxyethyldisulfanyl)ethane-1,1-diol Chemical compound OC(O)CSSCC(O)O APTMUIAOGSSQEM-UHFFFAOYSA-N 0.000 description 1
- MHGUSQPDQPUNQD-UHFFFAOYSA-N 2-(2,2-disulfoethyldisulfanyl)ethane-1,1-disulfonic acid Chemical compound OS(=O)(=O)C(S(O)(=O)=O)CSSCC(S(O)(=O)=O)S(O)(=O)=O MHGUSQPDQPUNQD-UHFFFAOYSA-N 0.000 description 1
- RXQXJZDPDXVIEN-UHFFFAOYSA-N 2-azaniumyl-3-(2-azaniumyl-2-carboxylatoethyl)sulfonylsulfanylpropanoate Chemical compound OC(=O)C(N)CSS(=O)(=O)CC(N)C(O)=O RXQXJZDPDXVIEN-UHFFFAOYSA-N 0.000 description 1
- UPPLJLAHMKABPR-UHFFFAOYSA-H 2-hydroxypropane-1,2,3-tricarboxylate;nickel(2+) Chemical compound [Ni+2].[Ni+2].[Ni+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O UPPLJLAHMKABPR-UHFFFAOYSA-H 0.000 description 1
- HSXUNHYXJWDLDK-UHFFFAOYSA-N 2-hydroxypropane-1-sulfonic acid Chemical class CC(O)CS(O)(=O)=O HSXUNHYXJWDLDK-UHFFFAOYSA-N 0.000 description 1
- YXEXMVJHQLWNGG-UHFFFAOYSA-N 3-(3,3-disulfopropyldisulfanyl)propane-1,1-disulfonic acid Chemical compound OS(=O)(=O)C(S(O)(=O)=O)CCSSCCC(S(O)(=O)=O)S(O)(=O)=O YXEXMVJHQLWNGG-UHFFFAOYSA-N 0.000 description 1
- RRQNLQWDRBLOLU-UHFFFAOYSA-N 5-(5,5-disulfopentyldisulfanyl)pentane-1,1-disulfonic acid Chemical compound OS(=O)(=O)C(S(O)(=O)=O)CCCCSSCCCCC(S(O)(=O)=O)S(O)(=O)=O RRQNLQWDRBLOLU-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- ADJYOCLYAFKVKH-UHFFFAOYSA-N C(CC)SSCCS(=O)(=O)O.[Na] Chemical compound C(CC)SSCCS(=O)(=O)O.[Na] ADJYOCLYAFKVKH-UHFFFAOYSA-N 0.000 description 1
- KHLBHOGUNFMIFP-UHFFFAOYSA-N CCCSSCCCCS(O)(=O)=O Chemical compound CCCSSCCCCS(O)(=O)=O KHLBHOGUNFMIFP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- GXIWMALOYDSQMW-UHFFFAOYSA-N ClCl(=O)=O Chemical compound ClCl(=O)=O GXIWMALOYDSQMW-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- UDIPTWFVPPPURJ-UHFFFAOYSA-M Cyclamate Chemical compound [Na+].[O-]S(=O)(=O)NC1CCCCC1 UDIPTWFVPPPURJ-UHFFFAOYSA-M 0.000 description 1
- YPWSLBHSMIKTPR-UHFFFAOYSA-N Cystathionine Natural products OC(=O)C(N)CCSSCC(N)C(O)=O YPWSLBHSMIKTPR-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- ILRYLPWNYFXEMH-UHFFFAOYSA-N D-cystathionine Natural products OC(=O)C(N)CCSCC(N)C(O)=O ILRYLPWNYFXEMH-UHFFFAOYSA-N 0.000 description 1
- LEVWYRKDKASIDU-QWWZWVQMSA-N D-cystine Chemical compound OC(=O)[C@H](N)CSSC[C@@H](N)C(O)=O LEVWYRKDKASIDU-QWWZWVQMSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 1
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 1
- ILRYLPWNYFXEMH-WHFBIAKZSA-N L-cystathionine Chemical compound [O-]C(=O)[C@@H]([NH3+])CCSC[C@H]([NH3+])C([O-])=O ILRYLPWNYFXEMH-WHFBIAKZSA-N 0.000 description 1
- JYXGIOKAKDAARW-UHFFFAOYSA-N N-(2-hydroxyethyl)iminodiacetic acid Chemical compound OCCN(CC(O)=O)CC(O)=O JYXGIOKAKDAARW-UHFFFAOYSA-N 0.000 description 1
- AZSIRDIDJUESHO-UHFFFAOYSA-N NC(CCCCSSCCCCC(N)N)N Chemical compound NC(CCCCSSCCCCC(N)N)N AZSIRDIDJUESHO-UHFFFAOYSA-N 0.000 description 1
- YGOWPYIPFROURH-UHFFFAOYSA-N NC(CCCSSCCCC(N)N)N Chemical compound NC(CCCSSCCCC(N)N)N YGOWPYIPFROURH-UHFFFAOYSA-N 0.000 description 1
- WOSGAAGZINXPOI-UHFFFAOYSA-N OC(CCCCSSCCCCC(O)O)O Chemical compound OC(CCCCSSCCCCC(O)O)O WOSGAAGZINXPOI-UHFFFAOYSA-N 0.000 description 1
- CJRGRYHXYMWWIQ-UHFFFAOYSA-N OC(CCCSSCCCC(O)O)O Chemical compound OC(CCCSSCCCC(O)O)O CJRGRYHXYMWWIQ-UHFFFAOYSA-N 0.000 description 1
- QMPQADPTQQZJCZ-UHFFFAOYSA-N OC(CCSSCCC(O)O)O Chemical compound OC(CCSSCCC(O)O)O QMPQADPTQQZJCZ-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- DIWBDBJGJBLYEM-UHFFFAOYSA-N [N+](=O)([O-])C(CSSCC([N+](=O)[O-])[N+](=O)[O-])[N+](=O)[O-] Chemical compound [N+](=O)([O-])C(CSSCC([N+](=O)[O-])[N+](=O)[O-])[N+](=O)[O-] DIWBDBJGJBLYEM-UHFFFAOYSA-N 0.000 description 1
- CFPOQLCRFIWTSJ-UHFFFAOYSA-N [Na].[Na].S(=O)(=O)(O)CCCSSCCCS(=O)(=O)O.[Na].[Na] Chemical compound [Na].[Na].S(=O)(=O)(O)CCCSSCCCS(=O)(=O)O.[Na].[Na] CFPOQLCRFIWTSJ-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 235000003704 aspartic acid Nutrition 0.000 description 1
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 1
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 1
- KYNFOMQIXZUKRK-UHFFFAOYSA-N bishydroxyethyldisulfide Natural products OCCSSCCO KYNFOMQIXZUKRK-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- BSXVKCJAIJZTAV-UHFFFAOYSA-L copper;methanesulfonate Chemical compound [Cu+2].CS([O-])(=O)=O.CS([O-])(=O)=O BSXVKCJAIJZTAV-UHFFFAOYSA-L 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229960003067 cystine Drugs 0.000 description 1
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 1
- WIYCQLLGDNXIBA-UHFFFAOYSA-L disodium;3-(3-sulfonatopropyldisulfanyl)propane-1-sulfonate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)CCCSSCCCS([O-])(=O)=O WIYCQLLGDNXIBA-UHFFFAOYSA-L 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- BLQJIBCZHWBKSL-UHFFFAOYSA-L magnesium iodide Chemical class [Mg+2].[I-].[I-] BLQJIBCZHWBKSL-UHFFFAOYSA-L 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-M methanesulfonate group Chemical class CS(=O)(=O)[O-] AFVFQIVMOAPDHO-UHFFFAOYSA-M 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- AIYYMMQIMJOTBM-UHFFFAOYSA-L nickel(ii) acetate Chemical compound [Ni+2].CC([O-])=O.CC([O-])=O AIYYMMQIMJOTBM-UHFFFAOYSA-L 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- KBFJUSPXGQWLBO-UHFFFAOYSA-N sodium;2-(2-sulfoethyldisulfanyl)ethanesulfonic acid Chemical compound [Na].[Na].OS(=O)(=O)CCSSCCS(O)(=O)=O KBFJUSPXGQWLBO-UHFFFAOYSA-N 0.000 description 1
- YHFVDOSLWFPNJU-UHFFFAOYSA-N sodium;4-(4-sulfobutyldisulfanyl)butane-1-sulfonic acid Chemical compound [Na].[Na].OS(=O)(=O)CCCCSSCCCCS(O)(=O)=O YHFVDOSLWFPNJU-UHFFFAOYSA-N 0.000 description 1
- DIKJULDDNQFCJG-UHFFFAOYSA-M sodium;prop-2-ene-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC=C DIKJULDDNQFCJG-UHFFFAOYSA-M 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- NJPKYOIXTSGVAN-UHFFFAOYSA-K trisodium;naphthalene-1,3,6-trisulfonate Chemical compound [Na+].[Na+].[Na+].[O-]S(=O)(=O)C1=CC(S([O-])(=O)=O)=CC2=CC(S(=O)(=O)[O-])=CC=C21 NJPKYOIXTSGVAN-UHFFFAOYSA-K 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/58—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
- B32B15/013—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
- C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
- C22C19/058—Alloys based on nickel or cobalt based on nickel with chromium without Mo and W
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
- C22C30/02—Alloys containing less than 50% by weight of each constituent containing copper
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
Un baño de galvanoplastia de aleación de cobre-níquel que comprende: (a) una sal de cobre y una sal de níquel; (b) un agente de complejación de metal; (c) una pluralidad de sales que proporcionan conductividad diferentes entre sí, en la que las sales que proporcionan conductividad (c) incluyen una sal de haluro inorgánico y una sal seleccionada del grupo que consiste en sulfatos inorgánicos y alcanosulfonatos inferiores; (d) un compuesto seleccionado del grupo que consiste en compuestos disulfuro, aminoácidos que contiene azufre, y sus sales; (e) un compuesto seleccionado del grupo que consiste en compuestos de ácido sulfónico, compuestos de sulfimida, compuestos de ácido sulfámico, sulfonamidas, y sus sales; y (f) un producto de reacción entre un glicidil éter y un alcohol polivalente, en el que el baño tiene un pH de 3 a 8.A copper-nickel alloy electroplating bath comprising: (a) a copper salt and a nickel salt; (b) a metal complexing agent; (c) a plurality of salts that provide conductivity different from each other, wherein the salts that provide conductivity (c) include an inorganic halide salt and a salt selected from the group consisting of inorganic sulfates and lower alkanesulfonates; (d) a compound selected from the group consisting of disulfide compounds, sulfur-containing amino acids, and their salts; (e) a compound selected from the group consisting of sulfonic acid compounds, sulfimide compounds, sulfamic acid compounds, sulfonamides, and their salts; and (f) a reaction product between a glycidyl ether and a polyvalent alcohol, in which the bath has a pH of 3 to 8.
Description
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DESCRIPCIONDESCRIPTION
Bano de galvanoplastia de aleacion de cobre-mquel y metodo de chapado Campo tecnicoCopper-nickel alloy electroplating plating and plating method Technical field
La presente invencion se refiere a un bano de galvanoplastia de aleacion cobre-mquel y un metodo de revestimiento. Mas espedficamente, la presente invencion se refiere a un bano de chapado que tiene una excelente estabilidad al bano y un metodo de chapado que son capaces de obtener un revestimiento chapado que tiene una composicion uniforme de cobre y mquel en cualquier relacion de aleacion sobre una pieza de trabajo.The present invention relates to a copper-nickel alloy electroplating bath and a coating method. More specifically, the present invention relates to a plating bath that has excellent bath stability and a plating method that are capable of obtaining a plated coating having a uniform composition of copper and nickel in any alloy relationship on a piece. of work.
Antecedentes de la tecnicaBackground of the technique
En general, las aleaciones de cobre-mquel presentan excelentes propiedades de resistencia a la corrosion, ductilidad, procesabilidad y alta temperatura al cambiar la relacion de cobre y mquel, y tambien tienen naturalazas caractensticas tales como resistividad electrica, coeficiente de resistividad termica, fuerza electromotriz termica y coeficiente de expansion termica. Por lo tanto, se han realizado estudios del pasado en el pasado para obtener tales propiedades de aleaciones cobre-mquel por galvanoplastia. Se han estudiado numerosos banos como un bano de cian, un bano de acido dtrico, un bano de acido acetico, un bano de acido tartarico, un bano de acido tiosulfurico, un bano de amomaco y un bano de acido pirofosforico, como el bano de aleacion de cobre-mquel que se ha intentado convencionalmente; sin embargo, ninguno se ha puesto en uso practico. Las razones por las que no se ha utilizado practicamente ningun chapado de aleacion cobre-mquel incluyen: (i) el cobre y el mquel difieren entre sf en el potencial de deposicion en aproximadamente 0,6 V, de manera que el cobre con preferencia se deposita; (ii) tal bano de chapado es inestable, de manera que se forma un compuesto insoluble tal como hidroxido metalico; similares. Los ejemplos banos de chapados de aleacion de cobre-mquel informados hasta ahora incluyen los siguientes.In general, copper-nickel alloys have excellent properties of corrosion resistance, ductility, processability and high temperature when changing the ratio of copper and nickel, and also have characteristic natures such as electrical resistivity, thermal resistivity coefficient, electromotive force thermal and thermal expansion coefficient. Therefore, past studies have been conducted in the past to obtain such copper-nickel alloys properties by electroplating. Numerous bathrooms have been studied such as a cyan bath, a dric acid bath, an acetic acid bath, a tartaric acid bath, a thiosulfuric acid bath, an amomaco bath and a pyrophosphoric acid bath, such as the bath of copper-nickel alloy that has been tried conventionally; however, none has been put into practical use. The reasons why virtually no copper-nickel alloy plating has been used include: (i) copper and nickel differ from each other in the deposition potential by approximately 0.6 V, so that copper is preferably deposit; (ii) such plating bath is unstable, so that an insoluble compound such as metal hydroxide is formed; Similar. Examples of copper-nickel alloy plating baths reported so far include the following.
(1) JP-A Sho 49-90234:(1) JP-A Sho 49-90234:
Un bano de galvanoplastia que contiene cobre, mquel, y acido borico a un pH de aproximadamente 1, con el cual se obtiene un chapado que tiene un contenido de cobre de 25%.An electroplating bath containing copper, nickel, and boric acid at a pH of approximately 1, with which a plating having a copper content of 25% is obtained.
(2) JP-A Sho 52-024133:(2) JP-A Sho 52-024133:
Un bano que contiene una mezcla de cobre, mquel, acido dtrico, y agua amoniacal, con el cual se obtiene un chapado que tiene cualquier composicion de aleacion.A bath containing a mixture of copper, nickel, dric acid, and ammonia water, with which a plating is obtained that has any alloy composition.
(3) JP-A Sho 58-133391:(3) JP-A Sho 58-133391:
Un bano a base de acido pirofosforico que contiene pirofosfato cuya concentracion se define, a la cual se anaden aditivos primarios y segundarios para obtener de este modo un chapado brillante.A pyrophosphoric acid-based bath containing pyrophosphate whose concentration is defined, to which primary and secondary additives are added to obtain a glossy plating.
4) JP-A Hei 2-285091:4) JP-A Hei 2-285091:
Un bano que contiene sulfato de mquel, cloruro de mquel, sulfato de cobre, citrato de sodio, acido borico, y ademas borato de sodio anadido al mismo, y que tiene un pH de 4 a 7.A bath containing nickel sulfate, nickel chloride, copper sulfate, sodium citrate, boric acid, and also sodium borate added thereto, and having a pH of 4 to 7.
(5) JP-A Hei 5-98488:(5) JP-A Hei 5-98488:
Un bano de acido debil que contiene cobre, mquel, tetraborato de sodio, sacarina, y un acido carboxflico tal como acido malico, acido gluconico y acido salidlico, con el cual se obtiene un chapado que tiene un contenido de cobre de 20 a 60% y un color cupromquel.A weak acid bath containing copper, nickel, sodium tetraborate, saccharin, and a carboxylic acid such as malic acid, gluconic acid and salidic acid, with which a plating having a copper content of 20 to 60% is obtained and a cupromquel color.
(6) JP-A Hei 6-173075:(6) JP-A Hei 6-173075:
Un bano de acido debil que contiene cobre, mquel, un acido aminocarboxflico, y heptonato de sodio, con el cual se obtiene un chapado que tiene un contenido de cobre de 18 a 64% y un color cupromquel.A weak acid bath containing copper, nickel, an aminocarboxylic acid, and sodium heptonate, with which a plating having a copper content of 18 to 64% and a cupromquel color is obtained.
Compendio de la invencionCompendium of the invention
Los revestimientos de la aleacion deseada se obtienen usando los banos de chapado con aleacion de cobre-mquel descriptos anteriormente.The coatings of the desired alloy are obtained using the copper-nickel alloy plating baths described above.
Sin embargo, existen algunos problemas que se deben resolver para obtener de forma estable que tiene revestimientos que tienen una composicion uniforme a nivel industrial.However, there are some problems that must be solved to obtain in a stable way that it has coatings that have a uniform composition at an industrial level.
(1) JP-A Sho 49-90234:(1) JP-A Sho 49-90234:
El bano es un bano de pH bajo (pH: aproximadamente 1) que no contiene agente complejante, y la composicion se obtiene mediante la adicion de una pequena cantidad de cobre a una gran cantidad de mquel. La deposicion preferencial de cobre no puede ser suprimida.The bath is a low pH bath (pH: approximately 1) that does not contain a complexing agent, and the composition is obtained by adding a small amount of copper to a large amount of nickel. The preferential deposition of copper cannot be suppressed.
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Por consiguiente, existe un problema de que la composicion de un revestimiento esta fuertemente influenciada por la densidad de corriente.Therefore, there is a problem that the composition of a coating is strongly influenced by the current density.
(2) JP-A Sho 52-024133:(2) JP-A Sho 52-024133:
Debido a que el bano contiene amomaco, el pH vana mucho. El bano es tal que si el pH es bajo (en un rango acido), es probable que cobre se deposite, y si el pH es alto (en un rango alcalino), es probable que se deposite mquel. El bano tiene un problema que, como el pH del bano vana, la composicion de un revestimiento galvanizado vana. Ademas, existe otro problema, debido a que el efecto de supresion de la deposicion de cobre preferencial es debil, la composicion de un revestimiento chapado es pobre en uniformidad debido a la influencia de la densidad de la corriente del catodo.Because the bath contains ammonia, the pH is very valuable. The bath is such that if the pH is low (in an acidic range), copper is likely to be deposited, and if the pH is high (in an alkaline range), it is likely to be deposited. The bathroom has a problem that, like the pH of the bathroom, the composition of a galvanized coating is empty. In addition, there is another problem, because the suppressive effect of preferential copper deposition is weak, the composition of a plated coating is poor in uniformity due to the influence of cathode current density.
(3) JP-A Sho 58-133391:(3) JP-A Sho 58-133391:
El bano de acido pirofosforico requiere pirofosfato en una cantidad molar dos veces o mas que la concentracion de metal en el bano. La concentracion de metal mquel en el bano esta restringida a 30 g/L o menos. En consecuencia, existen problemas de que la eficiencia de deposicion es baja y que el rango en el que se obtiene el brillo es estrecho.Pyrophosphoric acid bath requires pyrophosphate in a molar amount twice or more than the metal concentration in the bath. The concentration of metal in the bath is restricted to 30 g / L or less. Consequently, there are problems that the deposition efficiency is low and that the range in which the brightness is obtained is narrow.
(4) JP-A Hei 2-285091:(4) JP-A Hei 2-285091:
Debido a que la concentracion de mquel y la concentracion de cobre en el bano son altas, la accion de suprimir la deposicion preferencial de cobre es debil. Existe el problema de que si la densidad de la corriente del catodo esta en un rango bajo, el cobre se deposita preferentemente. Ademas, debido a que la concentracion de mquel y la concentracion de citrato de sodio en el bano son altas, esto provoca un problema de que el citrato de mquel insoluble precipita con el tiempo.Because the concentration of nickel and the concentration of copper in the bath are high, the action of suppressing the preferential deposition of copper is weak. There is a problem that if the density of the cathode current is in a low range, copper is preferentially deposited. Also, because the concentration of nickel and the concentration of sodium citrate in the bath are high, this causes a problem that the insoluble nickel citrate precipitates over time.
(5) JP-A Hei 5-98488:(5) JP-A Hei 5-98488:
La estabilidad en el tiempo del bano se mejora mediante la incorporacion de un acido carboxflico tal como acido malico, acido gluconico y acido salidlico, y se mejora el aspecto del revestimiento mediante la adicion de sacarina. Sin embargo, el bano tiene problemas de que el efecto de suprimir la deposicion preferencial de cobre es insuficiente y que la agitacion o similares provoca la deposicion de cobre preferencial.The stability over time of the bath is improved by the incorporation of a carboxylic acid such as malic acid, gluconic acid and salidic acid, and the appearance of the coating is improved by the addition of saccharin. However, the bath has problems that the effect of suppressing the preferential deposition of copper is insufficient and that agitation or the like causes the deposition of preferential copper.
(6) JP-A Hei 6-173075:(6) JP-A Hei 6-173075:
El bano de acido debil contiene cobre, mquel, un acido aminocarboxflico y heptonato de sodio, con lo que se obtiene un chapado que tiene un contenido de cobre de 18 a 64% y un color cupromquel. Sin embargo, existe el problema de que a medida que las concentraciones de cobre y mquel en el bano vanan, la composicion de un revestimiento galvanizado tambien vana mucho. Esto hace diffcil obtener un revestimiento que tiene una composicion estable.The weak acid bath contains copper, nickel, an aminocarboxylic acid and sodium heptonate, whereby a plating having a copper content of 18 to 64% and a cupromquel color is obtained. However, there is the problem that as the concentrations of copper and nickel in the bath go, the composition of a galvanized coating also varies greatly. This makes it difficult to obtain a coating that has a stable composition.
Ademas, existen problemas de que la agitacion reduce la accion de supresion de la deposicion de cobre preferencial y que la composicion del revestimiento depositado esta fuertemente influenciada por la densidad de la corriente del catodo.In addition, there are problems that agitation reduces the suppression action of the preferential copper deposition and that the composition of the deposited coating is strongly influenced by the density of the cathode current.
Un objeto de la presente invencion es proporcionar un bano de chapado con aleacion cobre-mquel y un metodo de chapado que resuelvan los problemas descriptos anteriormente de los banos de chapado convencionales y que sean capaces de obtener establemente un chapado que tenga cualquier composicion deseada sin precipitacion y similares, es menos probable que la composicion del revestimiento chapado sea influenciada por la densidad de la corriente catodica.An object of the present invention is to provide a plating bath with copper-nickel alloy and a plating method that solve the problems described above of conventional plating baths and that are capable of stably obtaining a plating that has any desired composition without precipitation. and the like, the plating coating composition is less likely to be influenced by the density of the cathode current.
La presente invencion proporciona un bano de galvanoplastia de aleacion de cobre-mquel que comprende: (a) una sal de cobre y una sal de mquel; (b) un agente de complejacion de metal; (c) una pluralidad de sales que proporcionan conductividad difieren entre sf, en el que las sales que proporcionan conductividad (c) incluyen una sal de haluro inorganico y una sal seleccionada del grupo que consiste en sulfatos inorganicos y alcanosulfonatos inferiores;The present invention provides a copper-nickel alloy electroplating bath comprising: (a) a copper salt and a nickel salt; (b) a metal complexing agent; (c) a plurality of salts that provide conductivity differ from each other, in which the salts that provide conductivity (c) include an inorganic halide salt and a salt selected from the group consisting of inorganic sulfates and lower alkanesulfonates;
(d) a compuesto seleccionado del grupo que consiste en compuestos disulfuro, aminoacidos que contiene azufre, y sus sales;(d) a compound selected from the group consisting of disulfide compounds, sulfur-containing amino acids, and their salts;
(e) un compuesto seleccionado del grupo que consiste en compuestos de acido sulfonico, compuestos de sulfimida, compuestos de acido sulfamico, sulfonamidas, y sus sales; y (f) un producto de reaccion entre un glicidil eter y un alcohol polivalente, en el que el bano tiene un pH de 3 a 8.(e) a compound selected from the group consisting of sulfonic acid compounds, sulfimide compounds, sulfamic acid compounds, sulfonamides, and their salts; and (f) a reaction product between a glycidyl ether and a polyvalent alcohol, in which the bath has a pH of 3 to 8.
Ademas, la presente invencion proporciona un metodo para galvanoplastia de un sustrato con una aleacion cobre- mquel, el sustrato se selecciona del grupo que consiste en sustratos metalicos de cobre, hierro, mquel, plata, oro y sus aleaciones, y sustratos de vidrio, ceramica y plastico cuyas superficies se modifican con cualquiera de los metales y aleaciones, el metodo que comprende la galvanoplastia mediante el uso del bano de galvanoplastia de aleacion de cobre-mquel de acuerdo con cualquiera de las reivindicaciones 1 a 7.In addition, the present invention provides a method for electroplating a substrate with a copper alloy, the substrate is selected from the group consisting of metal substrates of copper, iron, nickel, silver, gold and its alloys, and glass substrates, ceramic and plastic whose surfaces are modified with any of the metals and alloys, the method comprising electroplating by using the copper-nickel alloy electroplating bath according to any one of claims 1 to 7.
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La presente invencion hace posible proporcionar un bano de chapado con la aleacion de cobre-mquel y un metodo de chapado que son capaces de obtener de modo estable un chapado que tenga cualquier composicion sin precipitacion y similares, es menos probable que la composicion del revestimiento chapado sea influenciada por la densidad de corriente catodica.The present invention makes it possible to provide a plating bath with the copper-nickel alloy and a plating method that are capable of stably obtaining a plating having any composition without precipitation and the like, it is less likely that the plating coating composition is influenced by cathode current density.
Descripcion de las formas de realizacionDescription of the forms of realization
Un bano de galvanoplastia de aleacion de cobre-mquel de la presente invencion contiene (a) una sal de cobre y una sal de mquel, (b) un agente de complejacion de metal, (c) multiples sales que proporcionan conductividad diferente entre sf, en el que las sales que proporcionan conductividad (c) incluyen una sal de haluro inorganico y una sal seleccionada del grupo que consiste en sulfatos inorganicos y alcanosulfonatos inferiores, (d) un compuesto seleccionado del grupo que consiste en compuestos disulfuro, aminoacidos que contiene azufre, y sus sales, (e) un compuesto seleccionado del grupo que consiste en compuestos de acido sulfonico, compuestos de sulfimida, compuestos de acido sulfamico, sulfonamidas, y sus sales, y (f) un producto de reaccion entre un glicidil eter y un alcohol polivalente.A copper-nickel alloy electroplating bath of the present invention contains (a) a copper salt and a nickel salt, (b) a metal complexing agent, (c) multiple salts that provide different conductivity between sf, wherein the salts that provide conductivity (c) include an inorganic halide salt and a salt selected from the group consisting of inorganic sulfates and lower alkanesulfonates, (d) a compound selected from the group consisting of disulfide compounds, sulfur-containing amino acids , and its salts, (e) a compound selected from the group consisting of sulfonic acid compounds, sulfimide compounds, sulfamic acid compounds, sulfonamides, and their salts, and (f) a reaction product between a glycidyl ether and a polyvalent alcohol
(a) Sal de cobre y sal de mquel(a) Copper salt and nickel salt
La sal de cobre incluye sulfato de cobre, haluros de cobre(II), sulfamatos de cobre, metansulfonato de cobre, acetato de cobre(II, carbonato de cobre basico, y similares, pero no se limita a estos. Estas sales de cobre se pueden usar solos, o se pueden usar como una mezcla de dos o mas de estos. La sal de mquel incluye sulfato de mquel, haluros de mquel, carbonato de mquel basico, sulfamato de mquel, acetato de mquel, metansulfonato de mquel, y similares, pero no se limita a estos. Estas sales de mquel se pueden usar solas, o se pueden usar como una mezcla de dos o mas de estos. La concentracion de la sal de cobre y la sal de mquel en el bano de chapado se debe seleccionar de varias maneras de acuerdo con la composicion de un revestimiento chapado que se obtiene, pero es 0,5 a 40 g/L, preferentemente 2 a 30 g/L para ion cobre y 0,25 a 80 g/L, preferentemente 0,5 a 50 g/L para ion mquel.The copper salt includes copper sulfate, copper halides (II), copper sulfamates, copper methanesulfonate, copper acetate (II, basic copper carbonate, and the like, but not limited to these. These copper salts are they can be used alone, or they can be used as a mixture of two or more of these .. The nickel salt includes nickel sulfate, nickel halides, basic nickel carbonate, nickel sulfamate, nickel acetate, nickel methanesulfonate, and the like. , but not limited to these. These salts of nickel can be used alone, or can be used as a mixture of two or more of these. The concentration of copper salt and the salt of nickel in the plating bath should be select in various ways according to the composition of a plated coating that is obtained, but is 0.5 to 40 g / L, preferably 2 to 30 g / L for copper ion and 0.25 to 80 g / L, preferably 0 , 5 to 50 g / L for nickel ion.
(b) Agente de complejacion de metal(b) Metal complexing agent
El agente de complejacion de metal estabiliza los metales cobre y mquel. El agente de complejacion de metal incluyen acidos monocarboxflicos, acidos dicarboxflicos, acidos policarboxflicos, acidos oxicarboxflicos, acidos ceto- carboxflicos, aminoacidos, acidos aminocarboxflicos, sus sales, y similares, pero no se limita a estos. En forma espedfica, el agente de complejacion de metal incluye acido malonico, acido maleico, acido succmico, acido tricarbaftlico, acido cftrico, acido tartarico, acido malico, acido gluconico, acido 2-sulfoetilimino-N, N-diacetico,acido iminodiacetico, acido nitrilotriacetico, EDTA, acido trietilendiaminotetraacetico, acido hidroxietiliminodiacetico, acido glutamico, acido aspartico, acido p-alanina-N,N- diacetico, y similares. Entre estos, son preferibles acido malonico, acido cftrico, acido malico, acido gluconico, EDTA, acido nitrilotriacetico y acido glutamico. Ademas, las sales de estos acidos carboxflicos incluyen sales de magnesio, sales de sodio, sales de potasio, sales de amonio, y similares, pero no se limita a estos. Estos agentes de complejacion de metales se pueden usar solos, o se pueden usar como una mezcla de dos o mas de estos. La concentracion del el agente de complejacion de metal en el bano de chapado es preferentemente 0,6 a 2 veces, mas preferentemente 0,7 a 1,5 veces, la concentracion del ion metalico) en el bano.The metal complexing agent stabilizes the copper and nickel metals. The metal complexing agent includes monocarboxylic acids, dicarboxylic acids, polycarboxylic acids, oxycarboxylic acids, ketocarboxylic acids, amino acids, aminocarboxylic acids, their salts, and the like, but not limited thereto. Specifically, the metal complexing agent includes malonic acid, maleic acid, succinic acid, tricarbapholic acid, cfric acid, tartaric acid, maolic acid, gluconic acid, 2-sulfoethylimino-N, N-diacetic acid, iminodiacetic acid, acid nitrilotriacetic, EDTA, triethylenediaminetetraacetic acid, hydroxyethyliminodiacetic acid, glutamic acid, aspartic acid, p-alanine-N, N-diacetic acid, and the like. Among these, malonic acid, cfric acid, malic acid, gluconic acid, EDTA, nitrilotriacetic acid and glutamic acid are preferable. In addition, the salts of these carboxylic acids include magnesium salts, sodium salts, potassium salts, ammonium salts, and the like, but not limited to these. These metal complexing agents can be used alone, or they can be used as a mixture of two or more of these. The concentration of the metal complexing agent in the plating bath is preferably 0.6 to 2 times, more preferably 0.7 to 1.5 times, the concentration of the metal ion) in the bath.
(c) Sales que proporcionan conductividad(c) Salts that provide conductivity
Las sales que proporcionan conductividad proporcionan el bano de galvanoplastia con aleacion cobre-mquel con conductividad electrica. En la presente invencion, las sales que proporcionan conductividad usada para tener multiples sales que proporcionan conductividad y diferentes entre sf. Las sales que proporcionan conductividad incluyen una sal de haluro inorganico y una sal seleccionada del grupo que consiste en sulfatos inorganicos y alcanosulfonatos inferiores.The salts that provide conductivity provide the electroplating alloy with copper-nickel alloy with electrical conductivity. In the present invention, the salts that provide conductivity used to have multiple salts that provide conductivity and differ from each other. Salts that provide conductivity include an inorganic halide salt and a salt selected from the group consisting of inorganic sulfates and lower alkanesulfonates.
La sal de haluro inorganico incluye sales de cloruro, sales de bromuro, sales de yoduro de magnesio, sodio, potasio, y amonio, y similares, pero no se limita a estos. Estas sales de haluro inorganico se pueden usar solas, o se pueden usar como una mezcla de dos o mas de estos. La concentracion de la sal de haluro inorganico en el bano de chapado es preferentemente 0,1 a 2,0 mol/L, mas preferentemente 0,2 a 1,0 mol/L.The inorganic halide salt includes chloride salts, bromide salts, magnesium iodide salts, sodium, potassium, and ammonium, and the like, but is not limited to these. These inorganic halide salts can be used alone, or they can be used as a mixture of two or more of these. The concentration of the inorganic halide salt in the plating bath is preferably 0.1 to 2.0 mol / L, more preferably 0.2 to 1.0 mol / L.
Los sulfatos inorganicos incluyen sulfato de magnesio, sulfato de sodio, sulfato de potasio, sulfato de amonio, y similares, pero no se limita a estos. Estos sulfatos inorganicos se pueden usar solos, o se pueden usar como una mezcla de dos o mas de estos.Inorganic sulfates include magnesium sulfate, sodium sulfate, potassium sulfate, ammonium sulfate, and the like, but not limited to these. These inorganic sulfates can be used alone, or they can be used as a mixture of two or more of these.
Los alcanosulfonatos inferiores incluyen sales de magnesio, sales de sodio, sales de potasio, sales de amonio, y similares, y mas espedficamente incluye sales de magnesio, sodio, potasio, y amonio de acido metansulfonico o acido 2-hidroxipropansulfonico, y similares, pero no se limita a estos. Estos sulfonatos se pueden usar solos, o se pueden usar como una mezcla de dos o mas de estos.Lower alkanesulfonates include magnesium salts, sodium salts, potassium salts, ammonium salts, and the like, and more specifically includes salts of magnesium, sodium, potassium, and methanesulfonic acid or 2-hydroxypropanesulfonic acid, and the like, but It is not limited to these. These sulfonates can be used alone, or they can be used as a mixture of two or more of these.
La concentracion del sulfate y/o el sulfonato en el bano de chapado es preferentemente 0,25 a 1,5 mol/L, mas preferentemente 0,5 a 1,25 mol/L.The sulfate and / or sulphonate concentration in the plating bath is preferably 0.25 to 1.5 mol / L, more preferably 0.5 to 1.25 mol / L.
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(d) Compuesto seleccionado del grupo que consiste en compuestos disulfuro, aminoacidos que contiene azufre, y sus sales(d) Compound selected from the group consisting of disulfide compounds, sulfur-containing amino acids, and their salts
El compuesto seleccionado del grupo que consiste en compuestos disulfuro, aminoacidos que contiene azufre, y sus sales incluye, pero sin limitacion, compuestos disulfuro representados por una formula general (I), y similares:The compound selected from the group consisting of disulfide compounds, sulfur-containing amino acids, and their salts includes, but are not limited to, disulfide compounds represented by a general formula (I), and the like:
A-R1-S-S-R2-A (I)A-R1-S-S-R2-A (I)
donde R1 y R2 representan un grupo hidrocarbonado, y A representa un SOaNa, un grupo SO3H, un grupo OH, un grupo NH2 o un grupo NO2.where R1 and R2 represent a hydrocarbon group, and A represents a SOaNa, a SO3H group, an OH group, an NH2 group or a NO2 group.
El grupo hidrocarbonado es preferentemente un grupo alquileno, mas preferentemente un grupo alquileno que tiene 1 a 6 atomos de carbono. Los ejemplos espedficos de los compuestos disulfuro incluyen sulfoetil disulfuro de bis- sodio, sulfopropil disulfuro de bis-sodio, sulfopentil disulfuro bis-sodio, sulfohexil disulfuro bis-sodio, bis-sulfoetil disulfuro, bis-sulfopropil disulfuro, bis-sulfopentil disulfuro, bis-aminoetil disulfuro, bis-aminopropil disulfuro, bis- aminobutil disulfuro, bis-aminopentil disulfuro, bis-hidroxietil disulfuro, bis-hidroxipropil disulfuro, bis-hidroxibutil disulfuro, bis-hidroxipentil disulfuro, bis-nitroetil disulfuro, bis-nitropropil disulfuro, bis-nitrobutil disulfuro, sulfoetil propil disulfuro de sodio, sulfobutil propil disulfuro, y similares, pero no se limita a estos. Entre estos compuesto disulfuro, sulfopropil disulfuro bis-sodio, sulfobutil disulfuro bis-sodio, bis-aminopropil disulfuro son preferible.The hydrocarbon group is preferably an alkylene group, more preferably an alkylene group having 1 to 6 carbon atoms. Specific examples of the disulfide compounds include bis-sodium sulfoethyl disulfide, bis-sodium sulfopropyl disulfide bis-sodium sulfopethyl disulphide bis-sodium, bis-sulfoethyl disulfide, bis-sulfopropyl disulfide, bis-sulfopentyl disulfide, bis -aminoethyl disulfide, bis-aminopropyl disulfide, bis-aminobutyl disulfide, bis-aminopentyl disulfide, bis-hydroxyethyl disulfide, bis-hydroxypropyl disulfide, bis-hydroxybutyl disulfide, bis-hydroxypentyl disulfide, bis-nitroethyl disulfide, bis-nitropropyl disulfide nitrobutyl disulfide, sodium sulfoethyl propyl disulfide, sulfobutyl propyl disulfide, and the like, but not limited to these. Among these compound disulfide, sulfopropyl disulphide bis-sodium, sulfobutyl disulfide bis-sodium, bis-aminopropyl disulfide are preferable.
Los aminoacidos que contiene azufre incluyen, pero sin limitacion, aminoacidos que contiene azufre representado por una formula general (II), y similares:Sulfur-containing amino acids include, but are not limited to, sulfur-containing amino acids represented by a general formula (II), and the like:
R-S-(CH2)nCHNHCOOH (II)R-S- (CH2) nCHNHCOOH (II)
donde R representa un grupo hidrocarbonado, -H, o - (CH2)nCHNHCOOH, y cada n es de modo independiente 1 a 50.where R represents a hydrocarbon group, -H, or - (CH2) nCHNHCOOH, and each n is independently 1 to 50.
El grupo hidrocarbonado es preferentemente un grupo alquilo, mas preferentemente un grupo alquilo que tiene 1 a 6 atomos de carbono. Los ejemplos espedficos de los aminoacidos que contienen azufre incluyen metionina, cistina, cistema, metionina, disulfoxido de cistina, cistationina, y similares, pero no se limita a estos. Ademas, sus sales incluyen sulfatos, sales de haluro, metansulfonatos, sulfamatos, acetatos y similares, pero no se limita a estos.The hydrocarbon group is preferably an alkyl group, more preferably an alkyl group having 1 to 6 carbon atoms. Specific examples of sulfur-containing amino acids include methionine, cystine, cystem, methionine, cystine disulfoxide, cystathionine, and the like, but not limited to these. In addition, its salts include sulfates, halide salts, methanesulfonates, sulfamates, acetates and the like, but not limited to these.
Estos compuestos disulfuro, aminoacidos que contiene azufre, y sus sales se pueden usar solos, o se pueden usar como una mezcla de dos o mas de estos. La concentracion del compuesto seleccionado del grupo que consiste en compuestos disulfuro, aminoacidos que contiene azufre, y sus sales en el bano de chapado es preferentemente 0,02 a 10 g/L, mas preferentemente 0,1 a 5 g/L.These disulfide compounds, sulfur-containing amino acids, and their salts can be used alone, or they can be used as a mixture of two or more of these. The concentration of the compound selected from the group consisting of disulfide compounds, sulfur-containing amino acids, and their salts in the plating bath is preferably 0.02 to 10 g / L, more preferably 0.1 to 5 g / L.
(e) Compuesto seleccionado del grupo que consiste en acido sulfonico, compuestos de sulfimida, compuestos de acido sulfamico, sulfonamidas y sus sales(e) Compound selected from the group consisting of sulfonic acid, sulfimide compounds, sulfamic acid compounds, sulfonamides and their salts
El compuesto seleccionado del grupo que consiste en compuestos de acido sulfonico, compuestos de sulfimida, compuestos de acido sulfamico, sulfonamidas, y sus sales obtiene revestimiento galvanizada con aleacion cobre- mquel denso.The compound selected from the group consisting of sulfonic acid compounds, sulfimide compounds, sulfamic acid compounds, sulfonamides, and their salts obtains galvanized coating with dense copper-copper alloy.
Los compuestos de acido sulfonico y sus sales incluyen acidos sulfonicos aromaticos, acidos alquenosulfonicos, acidos alquinosulfonicos, sus sales, y similares, pero no se limita a estos. En forma espedfica, los compuestos de acido sulfonico y sus sales incluyen 1,5-naftalendisulfonato de sodio, 1,3,6-naftalentrisulfonato de sodio, 2-propen-l- sulfonato de sodio, y similares, pero no se limita a estos.The sulfonic acid compounds and their salts include aromatic sulfonic acids, alkennesulfonic acids, alkynesulfonic acids, their salts, and the like, but not limited to these. Specifically, the sulfonic acid compounds and their salts include sodium 1,5-naphthalenedisulfonate, sodium 1,3,6-naphthalenetrisulfonate, sodium 2-propen-l-sulfonate, and the like, but not limited to these .
Los compuestos de sulfimida y sus sales incluyen sulfimida benzoica (sacarina), sus sales, y similares, pero no se limita a estos. En forma espedfica, los compuestos de sulfimida y sus sales incluyen sacarina sodica, y similares, pero no se limita a estos.The sulfimide compounds and their salts include benzoic sulfimide (saccharin), their salts, and the like, but not limited to these. Specifically, sulfimide compounds and their salts include sodium saccharin, and the like, but is not limited to these.
Los compuestos de acido sulfamico y sus sales incluyen acesulfama potasio, N-ciclohexilsulfamato de sodio, y similares, pero no se limita a estos.The sulfamic acid compounds and their salts include acesulfama potassium, sodium N-cyclohexylsulfamate, and the like, but not limited to these.
Las sulfonamidas y sus sales incluyen para-toluensulfonamidas, y similares, pero no se limita a estos.Sulfonamides and their salts include para-toluenesulfonamides, and the like, but are not limited to these.
Estos compuestos de acido sulfonico, compuestos de sulfimida, compuestos de acido sulfamico, sulfonamidas, y sus sales se pueden usar solos, o se pueden usar como una mezcla de dos o mas de estos. La concentracion del compuesto seleccionado del grupo que consiste en compuestos de acido sulfonico, compuestos de sulfimida, compuestos de acido sulfamico, sulfonamidas, y sus sales en el bano de chapado es preferentemente 0,2 a 5 g/L, mas preferentemente 0,4 a 4 g/L.These sulfonic acid compounds, sulfimide compounds, sulfamic acid compounds, sulfonamides, and their salts can be used alone, or they can be used as a mixture of two or more of these. The concentration of the compound selected from the group consisting of sulfonic acid compounds, sulfimide compounds, sulfamic acid compounds, sulfonamides, and their salts in the plating bath is preferably 0.2 to 5 g / L, more preferably 0.4 at 4 g / L.
(f) Producto de reaccion entre glicidil eter y alcohol polivalente(f) Reaction product between glycidyl ether and polyvalent alcohol
El producto de reaccion entre un glicidil eter y un alcohol polivalente hace denso al revestimiento galvanizada con aleacion de cobre-mquel.The reaction product between a glycidyl ether and a polyvalent alcohol makes the galvanized coating with copper-nickel alloy dense.
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45Four. Five
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En el producto de reaccion entre un glicidil eter y un alcohol polivalente, el glicidil eter que sirve como la materia prima de reaccion incluye glicidil eter que contienen dos o mas grupos epoxi en las moleculas, glicidil eteres que contienen uno o mas grupos hidroxilo y uno o mas grupos epoxi en las moleculas, y similares, pero no se limita a estos. En forma espedfica, el glicidil eter incluye glicidol, glicerol poliglicidil eter, etilen glicol diglicidil eter, polietilen glicol diglicidil eter, polipropilen glicol diglicidil eter, sorbitol poliglicidil eter, y similares.In the reaction product between a glycidyl ether and a polyvalent alcohol, the glycidyl ether that serves as the reaction raw material includes glycidyl ether containing two or more epoxy groups in the molecules, glycidyl ethers containing one or more hydroxyl groups and one or more epoxy groups in the molecules, and the like, but not limited to these. Specifically, glycidyl ether includes glycidol, glycerol polyglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, sorbitol polyglycidyl ether, and the like.
El alcohol polivalente incluye etilen glicol, propilen glicol, glicerina, poliglicerina y similares, pero no se limita a estos.The polyvalent alcohol includes ethylene glycol, propylene glycol, glycerin, polyglycerin and the like, but is not limited to these.
El producto de reaccion entre el glicidil eter y el alcohol polivalente es preferentemente un polfmero soluble en agua obtenido por una reaccion de condensacion entre un grupo epoxi del glicidil eter y un grupo hidroxilo del alcohol polivalente.The reaction product between glycidyl ether and polyvalent alcohol is preferably a water soluble polymer obtained by a condensation reaction between an epoxy group of glycidyl ether and a hydroxyl group of polyvalent alcohol.
Los productos de reaccion entre estos glicidil eteres y el alcohol polivalente se pueden usar solos, o se pueden usar como una mezcla de dos o mas de estos. La concentracion del el producto de reaccion entre el glicidil eter y el alcohol polivalente en el bano de chapado es preferentemente 0,05 a 5 g/L, mas preferentemente 0,1 a 2 g/L.The reaction products between these glycidyl ethers and the polyvalent alcohol can be used alone, or they can be used as a mixture of two or more of these. The concentration of the reaction product between glycidyl ether and the polyvalent alcohol in the plating bath is preferably 0.05 to 5 g / L, more preferably 0.1 to 2 g / L.
El bano de galvanoplastia de aleacion de cobre-mquel de la presente invencion debe ajustar para tener un pH de 3 a 8, preferentemente pH de 4 a 7. El pH del bano de chapado se puede ajustar con acido sulfurico, acido clorlddrico, acido bromddrico, acido metansulfonico, hidroxido de sodio, hidroxido de potasio, agua amoniacal, etilendiamina, dietilentriamina, trietilentetramina, o similares.The copper-nickel alloy electroplating bath of the present invention should be adjusted to have a pH of 3 to 8, preferably pH of 4 to 7. The pH of the plating bath can be adjusted with sulfuric acid, chlorochloric acid, bromidic acid , methanesulfonic acid, sodium hydroxide, potassium hydroxide, ammonia water, ethylenediamine, diethylenetriamine, triethylenetetramine, or the like.
A continuacion, se describira un metodo de chapado que usa el bano de chapado de la presente invencion. Una pieza de trabajo que se puede galvanizar mediante el uso del bano de chapado de la presente invencion, incluye cobre, hierro, mquel, plata, sus aleaciones y similares. Ademas, un sustrato de vidrio, un sustrato de ceramica y un sustrato de plastico cuyas superficies estan modificadas con cualquiera de los metales y aleaciones, y similares tambien son efectivos.Next, a plating method using the plating bath of the present invention will be described. A workpiece that can be galvanized by using the plating bath of the present invention includes copper, iron, nickel, silver, its alloys and the like. In addition, a glass substrate, a ceramic substrate and a plastic substrate whose surfaces are modified with any of the metals and alloys, and the like are also effective.
Cuando se lleva a cabo la galvanoplastia, es posible utilizar, como un anodo, un anodo insoluble tal como carbono, platino o titanio chapado con platino. Alternativamente, se puede usar un anodo de aleacion cobre-mquel. Alternativamente, tambien se puede usar un anodo de aleacion cobre-mquel, un anodo que utiliza cobre y mquel en combinacion, y similares. Sin embargo, en este caso, es necesario controlar cuidadosamente la concentracion de metal en el bano mediante el examen de la eficiencia de deposicion del catodo y la eficiencia de disolucion del anodo..When electroplating is performed, it is possible to use, as an anode, an insoluble anode such as carbon, platinum or platinum plated titanium. Alternatively, a copper-nickel alloy anode can be used. Alternatively, a copper-nickel alloy anode, an anode that uses copper and nickel in combination, and the like can also be used. However, in this case, it is necessary to carefully control the concentration of metal in the bath by examining the efficiency of cathode deposition and the dissolution efficiency of the anode.
La temperatura del bano es generalmente de 15 a 60 °C, preferentemente de 20 a 50 °C. La densidad de corriente del catodo es generalmente 0,01 a A/dm2, preferentemente 0, 05 a 4,0 A/dm2. El tiempo de chapado depende del espesor requerido de un revestimiento, pero es generalmente de 1 a 180 minutos, preferentemente de 15 a 120 minutos.The bath temperature is generally 15 to 60 ° C, preferably 20 to 50 ° C. The current density of the cathode is generally 0.01 to A / dm2, preferably 0.05 to 4.0 A / dm2. The plating time depends on the required thickness of a coating, but is generally 1 to 180 minutes, preferably 15 to 120 minutes.
El lfquido en el bano puede ser agitado por aire, flujo de lfquido, o mecanicamente con un agitador de catodo o similar. El espesor se puede ajustar en un intervalo amplio pero es generalmente 0,5 a 50 pm, preferentemente 3 a 20 pm. Mientras se realiza la galvanoplastia, el pH del bano de chapado se debe mantener entre 3 y 8 utilizando el agente de ajuste de pH mencionado anteriormente.The liquid in the bath can be stirred by air, liquid flow, or mechanically with a cathode stirrer or the like. The thickness can be adjusted over a wide range but is generally 0.5 to 50 pm, preferably 3 to 20 pm. While electroplating is performed, the pH of the plating bath should be maintained between 3 and 8 using the pH adjusting agent mentioned above.
El uso del bano de chapado de la presente invencion permite al revestimiento metalico que se deposita tener una relacion de composicion cobre/mquel de 5/95 a 95/5.The use of the plating bath of the present invention allows the metallic coating that is deposited to have a copper / nickel composition ratio of 5/95 to 95/5.
Cuando se realiza el chapado, la pieza de trabajo se somete a un pretratamiento de acuerdo con un metodo convencional ya continuacion la etapa de chapado.When the plating is performed, the work piece is subjected to a pretreatment according to a conventional method and then the plating stage.
En la etapa de pretratamiento, se realiza al menos una operacion: limpieza con inmersion, lavado electrolftico de un catodo o un anodo, lavado con un acido y activacion. El lavado con agua se realiza entre cada dos operaciones sucesivas. Despues del chapado, solo es necesario que el revestimiento resultante se lave con agua o agua caliente, seguido de secado. Ademas, despues de realizar el chapado con la aleacion de cobre-mquel, tambien se puede llevar a cabo un tratamiento antioxidacion, chapado con estano, chapado con aleacion de estano o similares. El bano de chapado de la presente invencion se puede usar durante un penodo de tiempo largo sin reemplazar el lfquido, mediante el mantenimiento de cada componente del bano a un nivel constante mediante el uso de un agente de reposicion adecuado.In the pretreatment stage, at least one operation is carried out: cleaning with immersion, electrolytic washing of a cathode or an anode, washing with an acid and activation. Water washing is performed between every two successive operations. After plating, it is only necessary that the resulting coating be washed with water or hot water, followed by drying. In addition, after plating with the copper-nickel alloy, an antioxidation treatment, plating with tin, plating with tin alloy or the like can also be carried out. The plating bath of the present invention can be used for a long period of time without replacing the liquid, by maintaining each bath component at a constant level by using a suitable repositioning agent.
A continuacion, se describira la presente invencion basada en ejemplos. Sin embargo, la presente invencion no se limita a estos. La composicion del bano de chapado y las condiciones de chapado se puede alterar arbitrariamente de acuerdo con tales criterios que es posible obtener un revestimiento chapado con una composicion uniforme de cobre y mquel con cualquier relacion de aleacion en la pieza de trabajo deseada descripta anteriormente, y que se obtiene un chapado con la aleacion de cobre-mquel que tiene excelente estabilidad del bano.Next, the present invention will be described based on examples. However, the present invention is not limited to these. The composition of the plating bath and the plating conditions can be arbitrarily altered according to such criteria that it is possible to obtain a plated coating with a uniform composition of copper and nickel with any alloy relationship in the desired workpiece described above, and that a plating with the copper-nickel alloy is obtained that has excellent bath stability.
EjemplosExamples
(Ejemplos 1 a 7 y Ejemplos comparativos 1 a 7)(Examples 1 to 7 and Comparative Examples 1 to 7)
Para la evaluacion de la galvanoplastia en Ejemplos, se pieza de prueba usada fue una placa de hierro (SPCC) de 0,5 x 65 x 100 = cuya superficie se sello con una cinta de Teflon (marca registrada). La placa de hierro como pieza 5 de prueba se desengraso con Dasshi-39 5% p/v [fabricado por DIPSOL CHEMICALS Co., Ltd.] y a continuacion se lavo con un acido de acido clorhndrico al 10,5% p/p seguido de lavado electrolftico con NC-20 5% p/p [fabricado por DIPSOL CHEMICALS Co., Ltd.] y solucion de hidroxido sodico 7% p/v.For the evaluation of electroplating in Examples, the test piece used was an iron plate (SPCC) of 0.5 x 65 x 100 = whose surface was sealed with a Teflon tape (registered trademark). The iron plate as test piece 5 was degreased with Dasshi-39 5% w / v [manufactured by DIPSOL CHEMICALS Co., Ltd.] and then washed with a 10.5% w / w hydrochloric acid followed of electrolytic washing with NC-20 5% w / w [manufactured by DIPSOL CHEMICALS Co., Ltd.] and 7% w / v sodium hydroxide solution.
Despues del lavado electrolftico, se activo la placa de hierro con acido clorhftdrico 3,5%. El lavado con agua se realizo suficientemente entre cada dos operaciones sucesivas. A continuacion, cada ftquido de chapado mostrado en 10 la Tabla 1 se introdujo en un tanque de chapado hecho de una resina acnlica. Se utilizo una placa de platino como anodo, y la placa de hierro activada anteriormente como pieza de prueba se conecto a un catodo. El chapado se llevo a cabo en las condiciones de la Tabla 2. El espesor y la composicion de aleacion del chapado obtenido se determinaron con un espectrometro de fluorescencia de rayos X. La Tabla-3 muestra el resultado.After electrolytic washing, the iron plate was activated with 3.5% hydrochloric acid. Water washing was sufficiently performed between every two successive operations. Next, each plating liquid shown in Table 1 was introduced into a plating tank made of an acrylic resin. A platinum plate was used as an anode, and the previously activated iron plate as a test piece was connected to a cathode. The plating was carried out under the conditions of Table 2. The thickness and alloy composition of the plating obtained were determined with an X-ray fluorescence spectrometer. Table-3 shows the result.
Asimismo en los Ejemplos comparativos, el chapado se llevo a cabo de la misma manera que en los Ejemplos en las 15 condiciones mostradas en la Tabla 5 usando ftquidos de chapado con composiciones mostradas en la Tabla-4. El espesor y la composicion de aleacion del chapado obtenido se determinaron con un espectrometro de fluorescencia de rayos X. La Tabla 6 muestra el resultado.Also in the Comparative Examples, plating was carried out in the same manner as in the Examples under the conditions shown in Table 5 using plating liquids with compositions shown in Table-4. The thickness and alloy composition of the plating obtained were determined with an X-ray fluorescence spectrometer. Table 6 shows the result.
Tabla-1 Composiciones de los banos de chapados de los EjemplosTable-1 Compositions of the plating baths of the Examples
- Concentraciones de los componentes Component Concentrations
- Ejemplo Example
- 1 one
- 2 3 4 5 6 7 2 3 4 5 6 7
- (a) Cu2+ (g/L) (a) Cu2 + (g / L)
- 3 25 9 7,5 7,5 7,5 5 3 25 9 7.5 7.5 7.5 5
- (a) Ni2+ (g/L) (a) Ni2 + (g / L)
- 50 40 20 15 7,5 7,5 1 50 40 20 15 7.5 7.5 1
- concentracion de metal (mol/L) (Cu2+ + Ni2+) metal concentration (mol / L) (Cu2 + + Ni2 +)
- 0,9 1,1 0,5 0,37 0,25 0,25 0,1 0.9 1.1 0.5 0.37 0.25 0.25 0.1
- (b) acido malonico (mol/L) (b) malonic acid (mol / L)
- 0,6 0,55 - 0,07 0.6 0.55 - 0.07
- (b) citrato de diamonio (mol/L) (b) diamonium citrate (mol / L)
- 0,8 - 0,2 - - 0.8 - 0.2 - -
- (b) acido nitrilotriacetico (mol/L) (b) nitrilotriacetic acid (mol / L)
- - 1,1 - 0,2 - - 1.1 - 0.2 -
- razon de concentracion molar agente de complejacion de metal/metal (coeficiente ) Molar concentration ratio metal / metal complexing agent (coefficient)
- 0,9 1,0 1,2 1,5 0,8 0,8 0,7 0.9 1.0 1.2 1.5 0.8 0.8 0.7
- (c) cloruro de sodio (mol/L) (c) sodium chloride (mol / L)
- - 0,75 - 0,5 - 0,6 0,5 - 0.75 - 0.5 - 0.6 0.5
- (c) bromuro de potasio (mol/L) (c) potassium bromide (mol / L)
- 1 - 0,2 - 0,25 - - 1 - 0.2 - 0.25 - -
- (c) sulfato de magnesio (mol/L) (c) magnesium sulfate (mol / L)
- - 0,5 - 1 0,9 0,8 - 0.5 - 1 0.9 0.8
- (c) metansulfonato de amonio (mol/L) (c) ammonium methanesulfonate (mol / L)
- 1 - 1,25 - 0,75 - - 1 - 1.25 - 0.75 - -
- (d) sulfopropil disulfuro bis-sodio (g/L) (d) Sulfopropyl disulfide bis-sodium (g / L)
- - 2 1 2,5 0,1 - 2 1 2.5 0.1
- (d) metansulfonato de cistema (g/L) (d) cystem methanesulfonate (g / L)
- 5 — 0,5 — 0,2 — — 5 - 0.5 - 0.2 - -
- (e) 1,5-naftalendisulfonato de sodio (g/L) (e) sodium 1,5-naphthalenedisulfonate (g / L)
- — 0,5 4 0,4 — 0,6 - 0.5 4 0.4 - 0.6
- (e) sacarina sodica (g/L) (e) sodium saccharin (g / L)
- 2 0,5 — 1 1,5 — 2 0.5 - 1 1.5 -
- (f) producto de reaccion de etilen glicol diglicidil eter con propilen glicol (g/L) (f) reaction product of ethylene glycol diglycidyl ether with propylene glycol (g / L)
- — 1 0,25 — 1 0,25 - 1 0.25 - 1 0.25
- (f) producto de reaccion de glicerol poliglicidil eter con poliglicerina(g/L) (f) reaction product of glycerol polyglycidyl ether with polyglycerin (g / L)
- 2 — 1,5 — 0,1 — — 2 - 1.5 - 0.1 - -
- pH pH
- 4 5 5 5 8 7 6 4 5 5 5 8 7 6
- Especies de sal de cobre: metansulfonato de cobre(II) (Ejemplos 1 y 5) , sulfato de cobre(II) (Ejemplos 2 y 4), sulfamato de cobre(II) (Ejemplo 3), acetato de cobre(II) (Ejemplo 6), cloruro de cobre(II) (Ejemplo 7) Especies de sal de mquel: metansulfonato de mquel (Ejemplos 1 y 5), sulfato de mquel (Ejemplos 2 y 4), sulfamato de mquel (Ejemplo 3), acetato de mquel (Ejemplo 6), cloruro de mquel (Ejemplo 7) Agente de ajuste de pH: acido metansulfonico (Ejemplo 1), hidroxido de sodio (Ejemplos 2, 4, 6, y 7), hidroxido de potasio (Ejemplo 3), agua amoniacal (Ejemplo 5) Copper salt species: copper (II) methanesulfonate (Examples 1 and 5), copper (II) sulfate (Examples 2 and 4), copper (II) sulfamate (Example 3), copper (II) acetate ( Example 6), copper (II) chloride (Example 7) Species of nickel salt: nickel methanesulfonate (Examples 1 and 5), nickel sulfate (Examples 2 and 4), nickel sulfamate (Example 3), acetate nickel (Example 6), nickel chloride (Example 7) pH adjusting agent: methanesulfonic acid (Example 1), sodium hydroxide (Examples 2, 4, 6, and 7), potassium hydroxide (Example 3), water ammoniacal (Example 5)
Tabla-2 Condiciones de chapado de los EjemplosTable-2 Plating Conditions of the Examples
- Artfculos Items
- Ejemplo Example
- 1 one
- 2 3 4 5 6 7 2 3 4 5 6 7
- tiempo de chapado (min.) plating time (min.)
- Densidad de corriente del catodo (A/dm2) Current density of the cathode (A / dm2)
- 0,5 0.5
- 120 120
- 2 2
- 30 30
- 5 5
- 10 10
- temperatura del bano (°C) bath temperature (° C)
- 50 50 50 25 25 25 50 50 50 50 25 25 25 50
- agitacion agitation
- con agitacion & sin agitacion with agitation & without agitation
Tabla-3 Resultados obtenidos en los EjemplosTable-3 Results obtained in the Examples
- Densidad de Ejemplo Density of Example
- Artfculos Items
- corriente del catodo (A/dm2) 1 2 3 4 5 6 7 cathode current (A / dm2) 1 2 3 4 5 6 7
- espesor thickness
- 0,5 13 13 12 12 12 12 12 0.5 13 13 12 12 12 12 12
- (Pm) (P.m)
- 2 12 12 11 11 11 11 10 2 12 12 11 11 11 11 10
- con agitacion with agitation
- 5 9 9 8,5 8,5 8,5 8,5 8 5 9 9 8.5 8.5 8.5 8.5 8
- composicion composition
- 0,5 9 25 44 62 79 79 88 0.5 9 25 44 62 79 79 88
- de from
- 2 10 22 42 60 80 80 91 2 10 22 42 60 80 80 91
- revestimiento (Cu %) sin agitacion coating (Cu%) without stirring
- 5 11 20 40 60 81 81 92 5 11 20 40 60 81 81 92
- composicion de revestimiento (Cu %) con agitacion coating composition (Cu%) with stirring
- 0,5 9 25 45 61 79 80 88 0.5 9 25 45 61 79 80 88
- 2 2
- 10 22 42 61 80 80 91 10 22 42 61 80 80 91
- 5 5
- 8 20 40 58 82 81 92 8 20 40 58 82 81 92
- aspecto con agitacion agitated appearance
- 0,5 blanco plateado blanco plateado blanco plateado blanco plateado color cupromquel color cupromquel cupromquel palido 0.5 white silver white silver white white silver white silver color cupromquel color cupromquel color cupromquel pale
- 2 2
- brillante brillante brillante brillante semi- brillante semi- brillante color semi- brillante bright bright bright bright semi-bright semi-bright semi-bright color
- blanco plateado brillante shiny silver white
- blanco plateado brillante shiny silver white
- blanco plateado brillante shiny silver white
- blanco plateado brillante shiny silver white
- color cupromquel semi- brillante color cupromquel semi- brillante color cupromquel palido semi- brillante semi-bright cupromquel color semi-bright cupromquel color semi-bright pale cupromquel color
- 5 5
- blanco plateado brillante blanco plateado brillante blanco plateado brillante blanco plateado brillante color cupromquel semi- brillante color cupromquel semi- brillante color cupromquel palido semi- brillante white silver glossy white silver glossy white silver glossy white silver glossy color semi-bright cupromquel color semi-bright cupromquel color semi-bright pale cupromquel color
- estabilidad del bano de chapado formacion de turbiedad precipita despues de dejar decantar durante 7 dfas a temperatura ambiente stability of the plating bath turbidity formation precipitates after allowing to decant for 7 days at room temperature
- ninguno ninguno ninguno ninguno ninguno ninguno ninguno none none none none none none none
Tabla-4 Composiciones de bano de chapados de los ejemplos comparativosTable-4 Plating bath compositions of the comparative examples
- concentraciones de componentes component concentrations
- Ejemplo comparativo Comparative example
- 1 one
- 2 3 4 5 6 7 2 3 4 5 6 7
- (a) Cu2+ (g/L) (a) Cu2 + (g / L)
- 3 25 9 7,5 7,5 7,5 5 3 25 9 7.5 7.5 7.5 5
- (a) Ni2+ (g/L) (a) Ni2 + (g / L)
- 50 40 20 15 7,5 7,5 1 50 40 20 15 7.5 7.5 1
- concentracion de metal (mol/L) (Cu2+ + Ni2+) metal concentration (mol / L) (Cu2 + + Ni2 +)
- 0,9 1,1 0,5 0,37 0,25 0,25 0,1 0.9 1.1 0.5 0.37 0.25 0.25 0.1
- (b) acido malonico (mol/L) (b) malonic acid (mol / L)
- - - 0,6 0,55 - 0,07 - - 0.6 0.55 - 0.07
- (b) citrato de diamonio(mol/L) (b) diamonium citrate (mol / L)
- 0,8 - - - 0,2 - - 0.8 - - - 0.2 - -
- (b) acido nitrilotriacetico (mol/L) (b) nitrilotriacetic acid (mol / L)
- - 1,1 - - - 0,2 - - 1,1 - - - 0,2 -
- agente de complejacion de relacion de concentracion molar metal/metal (cambio) metal / metal molar concentration ratio complexing agent (change)
- 0,9 1,0 1,2 1,5 0,8 0,8 0,7 0.9 1.0 1.2 1.5 0.8 0.8 0.7
- (c) cloruro de sodio (mol/L) (c) sodium chloride (mol / L)
- - 0,75 0,5 - 0,5 - 0.75 0.5 - 0.5
- (c) bromuro de potasio (mol/L) (c) potassium bromide (mol / L)
- 1 - 0,2 - 0,25 - 1 - 0.2 - 0.25 -
- (c) sulfato de magnesio (mol/L) (c) magnesium sulfate (mol / L)
- - 0,5 - 1 0,9 - - 0.5 - 1 0.9 -
- (c) metansulfonato de amonio (mol/L) (c) ammonium methanesulfonate (mol / L)
- 1 - 1,25 0,75 - 1 - 1.25 0.75 -
- (d) sulfopropil disulfuro de bis-sodio (g/L) (d) bis-sodium sulfopropyl disulfide (g / L)
- - 2 - 1 - 2,5 0,1 - 2 - 1 - 2.5 0.1
- (d) metansulfonato de cistema (g/L) (d) cystem methanesulfonate (g / L)
- — — — — — — — - - - - - - -
- (e) 1,5-naftalendisulfonato de sodio (g/L) (e) sodium 1,5-naphthalenedisulfonate (g / L)
- — 0,5 4 0,4 — 0,6 - 0.5 4 0.4 - 0.6
- (e) sacarina sodica (g/L) (e) sodium saccharin (g / L)
- — 0,5 — 1,5 — - 0.5 - 1.5 -
- (f) producto de reaccion de etilen glicol diglicidil eter con propilen glicol (g/L) (f) reaction product of ethylene glycol diglycidyl ether with propylene glycol (g / L)
- — — — 0,25 1 0,25 - - - 0.25 1 0.25
- (f) producto de reaccion de glicerol poliglicidil eter con poliglicerina (g/L) (f) reaction product of glycerol polyglycidyl ether with polyglycerin (g / L)
- — — 1,5 — - - 1,5 -
- pH pH
- 4 5 5 5 8 7 6 4 5 5 5 8 7 6
- Especies de sal de cobre: metansulfonato de cobre(II) (Ejemplos comparativos 1 y 5), sulfato de cobre(II) (Ejemplos comparativos 2 y 4), sulfamato de cobre(II) (Ejemplo comparativo 3), acetato de cobre(II) (Ejemplo comparativo 6), cloruro de cobre(II) (Ejemplo comparativo 7) Copper salt species: copper (II) methanesulfonate (Comparative examples 1 and 5), copper (II) sulfate (Comparative examples 2 and 4), copper (II) sulfamate (Comparative example 3), copper acetate ( II) (Comparative example 6), copper (II) chloride (Comparative example 7)
- Especies de sales de mquel: metansulfonato de mquel (Ejemplos comparativos 1 y 5), sulfato de mquel (Ejemplos comparativos 2 y 4), sulfamato de mquel (Ejemplo comparativo 3), acetato de mquel (Ejemplo comparativo 6), cloruro de mquel (Ejemplo comparativo 7) Species of nickel salts: nickel methanesulfonate (Comparative examples 1 and 5), nickel sulfate (Comparative examples 2 and 4), nickel sulfamate (Comparative example 3), nickel acetate (Comparative example 6), nickel chloride ( Comparative Example 7)
- agente de ajuste de pH: acido metansulfonico (Ejemplo comparativo 1), hidroxido de sodio (Ejemplos comparativos 2, 4, 6, y 7), hidroxido de potasio (Ejemplo comparativo 3), agua amoniacal (Ejemplo comparativo 5) pH adjusting agent: methanesulfonic acid (Comparative example 1), sodium hydroxide (Comparative examples 2, 4, 6, and 7), potassium hydroxide (Comparative example 3), ammonia water (Comparative example 5)
Tabla-5 Condiciones de chapado de los ejemplos comparativosTable-5 Plating conditions of comparative examples
- Artfculos Items
- Ejemplo comparativo Comparative example
- 1 one
- 2 3 4 5 6 7 2 3 4 5 6 7
- tiempo de chapado (min.) plating time (min.)
- Densidad de corriente catodica (A/dm2) Density of cathode current (A / dm2)
- 0,5 0.5
- 120 120
- 2 2
- 30 30
- 5 5
- 10 10
- temperatura del bano (°C) bath temperature (° C)
- 50 50 50 25 25 25 50 50 50 50 25 25 25 50
- agitacion agitation
- con agitacion & sin agitacion with agitation & without agitation
Tabla-6 Resultados obtenidos en los ejemplos comparativosTable-6 Results obtained in the comparative examples
- Artfculos Items
- Densidad de Ejemplo comparativo Density of Comparative Example
- corriente catodica (A/dm2) 1 2 3 4 5 6 7 cathode current (A / dm2) 1 2 3 4 5 6 7
- espesor thickness
- 0,5 13 13 12 12 12 12 12 0.5 13 13 12 12 12 12 12
- (pm) con agitacion (pm) with agitation
- 2 12 12 11 11 11 11 10 2 12 12 11 11 11 11 10
- 5 5
- 9 9 8,5 8,5 8,5 8,5 8 9 9 8.5 8.5 8.5 8.5 8
- composicion de composition of
- 0,5 100 95 55 75 88 69 83 0.5 100 95 55 75 88 69 83
- revestimiento coating
- 2 0 22 41 60 83 77 91 2 0 22 41 60 83 77 91
- (Cu %) sin agitacion (Cu%) without agitation
- 5 0 18 38 55 79 81 95 5 0 18 38 55 79 81 95
- composicion de composition of
- 0,5 100 100 80 90 93 65 80 0.5 100 100 80 90 93 65 80
- revestimiento (Cu %) coating (Cu%)
- 2 0 22 42 63 83 74 89 2 0 22 42 63 83 74 89
- con agitacion with agitation
- 5 0 18 40 56 79 81 95 5 0 18 40 56 79 81 95
- aspecto con agitacion agitated appearance
- 0,5 deposito bruto de rojo de cobre deposito bruto de rojo de cobre color cupromquel no brillante deposito bruto de rojo de cobre deposito bruto de rojo de cobre deposito bruto de rojo de cobre color cupromquel no brillante 0.5 gross deposit of copper red gross deposit of copper red non-bright cupromquel color gross deposit of copper red gross deposit of copper red gross deposit of copper red non-bright copper color
- 2 blanco plateado brillante blanco plateado brillante blanco plateado brillante blanco plateado brillante color cupromquel no brillante color cupromquel semi- brillante cobre red no brillante 2 white silvery glossy white silvery glossy white silvery glossy white silvery glossy color non-glossy copper color semi-glossy copper color non-glossy red copper
- 5 blanco plateado brillante blanco plateado brillante blanco plateado brillante blanco plateado brillante color cupromquel no brillante color cupromquel no brillante cobre red no brillante 5 white silver glossy white silver glossy white silver glossy white silver glossy color cupromquel not glossy color cupromquel not glossy copper net not glossy
- estabilidad del bano de chapado plating bath stability
- ninguno ninguno ninguno ninguno ninguno ninguno ninguno none none none none none none none
- formacion de turbiedad turbidity formation
- precipita despues de dejar decantar durante 7 d^as a precipitates after letting decant for 7 days
- temperatura ambiente room temperature
Claims (12)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012095956 | 2012-04-19 | ||
| JP2012095956 | 2012-04-19 | ||
| PCT/JP2013/061667 WO2013157639A1 (en) | 2012-04-19 | 2013-04-19 | Copper-nickel alloy electroplating bath and plating method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| ES2620115T3 true ES2620115T3 (en) | 2017-06-27 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| ES13779037.4T Active ES2620115T3 (en) | 2012-04-19 | 2013-04-19 | Copper-nickel alloy electroplating bath and plating method |
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| Country | Link |
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| US (1) | US9828686B2 (en) |
| EP (1) | EP2840169B1 (en) |
| JP (1) | JP6119053B2 (en) |
| KR (1) | KR101649435B1 (en) |
| CN (1) | CN104321470B (en) |
| BR (1) | BR112014026009A2 (en) |
| ES (1) | ES2620115T3 (en) |
| IN (1) | IN2014MN01920A (en) |
| MX (1) | MX355999B (en) |
| MY (1) | MY167239A (en) |
| PH (1) | PH12014502330B1 (en) |
| RU (1) | RU2588894C2 (en) |
| SG (1) | SG11201406599RA (en) |
| TW (1) | TWI580822B (en) |
| WO (1) | WO2013157639A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015060449A1 (en) * | 2013-10-25 | 2015-04-30 | オーエム産業株式会社 | Method for producing plated article |
| JP6439172B2 (en) * | 2014-08-08 | 2018-12-19 | ディップソール株式会社 | Copper-nickel alloy electroplating bath |
| JP6435546B2 (en) | 2014-10-17 | 2018-12-12 | ディップソール株式会社 | Copper-nickel alloy electroplating equipment |
| CN104911656A (en) * | 2015-06-13 | 2015-09-16 | 梁胜光 | Metal alloy electroplating liquid |
| CN105018986A (en) * | 2015-08-11 | 2015-11-04 | 江苏金曼科技有限责任公司 | Cyanide-free and phosphorus-free alloy bottoming liquid |
| CN105506686A (en) * | 2015-12-23 | 2016-04-20 | 苏州市金星工艺镀饰有限公司 | Electroplating method for decorative nickel-copper-gold ternary alloy electroplating bath |
| JP6806093B2 (en) * | 2016-01-29 | 2021-01-06 | 住友金属鉱山株式会社 | Blackening plating solution, manufacturing method of conductive substrate |
| CN108495749B (en) * | 2016-01-29 | 2021-02-26 | 住友金属矿山株式会社 | Conductive substrate |
| JP6796243B2 (en) * | 2016-04-30 | 2020-12-09 | 日本製鉄株式会社 | Mechanical parts coated with copper-nickel alloy material |
| CN106283132B (en) * | 2016-08-26 | 2018-07-10 | 湖北吉和昌化工科技有限公司 | A kind of soft dispersant of subacidity system electroplating bright copper |
| US10711360B2 (en) * | 2017-07-14 | 2020-07-14 | Rohm And Haas Electronic Materials Llc | Nickel electroplating compositions with copolymers of arginine and bisepoxides and methods of electroplating nickel |
| JP2019044231A (en) * | 2017-09-01 | 2019-03-22 | 株式会社Ｊｃｕ | Electroplating solution for iron-nickel alloy having low thermal expansion coefficient and electroplating method using the same |
| US10205170B1 (en) * | 2017-12-04 | 2019-02-12 | Chang Chun Petrochemical Co., Ltd. | Copper foil for current collector of lithium secondary battery |
| CN110607541B (en) * | 2019-08-17 | 2021-07-16 | 山东理工大学 | A kind of copper-nickel composite electrode for EDM diamond and preparation method thereof |
| CN111321437B (en) * | 2020-03-31 | 2021-04-27 | 安徽铜冠铜箔集团股份有限公司 | Copper-nickel alloy foil and preparation method thereof by electrodeposition |
| CN114214677A (en) * | 2021-12-30 | 2022-03-22 | 佛山亚特表面技术材料有限公司 | Acidic copper plating deep hole agent, preparation method thereof and electroplating method |
| CN115787053B (en) * | 2022-11-21 | 2024-11-12 | 南通赛可特电子有限公司 | A highly stable electroplating additive and preparation method thereof |
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| US3338804A (en) * | 1964-09-03 | 1967-08-29 | Kewanee Oil Co | Electrodeposition of stress-free metal deposits |
| US3833481A (en) | 1972-12-18 | 1974-09-03 | Buckbel Mears Co | Electroforming nickel copper alloys |
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| KR100485808B1 (en) * | 2002-01-30 | 2005-04-28 | 한현섭 | electroplating bath for copper-nickel alloy and method for manufacturing thin film using said electroplating bath |
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-
2013
- 2013-04-19 WO PCT/JP2013/061667 patent/WO2013157639A1/en not_active Ceased
- 2013-04-19 US US14/395,776 patent/US9828686B2/en active Active
- 2013-04-19 EP EP13779037.4A patent/EP2840169B1/en active Active
- 2013-04-19 JP JP2014511260A patent/JP6119053B2/en active Active
- 2013-04-19 MY MYPI2014002954A patent/MY167239A/en unknown
- 2013-04-19 MX MX2014012027A patent/MX355999B/en active IP Right Grant
- 2013-04-19 IN IN1920MUN2014 patent/IN2014MN01920A/en unknown
- 2013-04-19 ES ES13779037.4T patent/ES2620115T3/en active Active
- 2013-04-19 KR KR1020147027765A patent/KR101649435B1/en active Active
- 2013-04-19 CN CN201380020656.3A patent/CN104321470B/en active Active
- 2013-04-19 BR BR112014026009A patent/BR112014026009A2/en not_active Application Discontinuation
- 2013-04-19 RU RU2014146285/02A patent/RU2588894C2/en active
- 2013-04-19 SG SG11201406599RA patent/SG11201406599RA/en unknown
- 2013-04-19 TW TW102114163A patent/TWI580822B/en active
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- 2014-10-17 PH PH12014502330A patent/PH12014502330B1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2013157639A1 (en) | 2015-12-21 |
| RU2014146285A (en) | 2016-06-10 |
| RU2588894C2 (en) | 2016-07-10 |
| CN104321470A (en) | 2015-01-28 |
| MX355999B (en) | 2018-05-08 |
| EP2840169A4 (en) | 2015-12-30 |
| TW201402878A (en) | 2014-01-16 |
| BR112014026009A2 (en) | 2017-06-27 |
| KR20140130546A (en) | 2014-11-10 |
| MX2014012027A (en) | 2014-12-05 |
| EP2840169A1 (en) | 2015-02-25 |
| EP2840169B1 (en) | 2017-03-01 |
| SG11201406599RA (en) | 2014-11-27 |
| TWI580822B (en) | 2017-05-01 |
| PH12014502330A1 (en) | 2015-01-12 |
| KR101649435B1 (en) | 2016-08-19 |
| IN2014MN01920A (en) | 2015-07-10 |
| MY167239A (en) | 2018-08-14 |
| CN104321470B (en) | 2017-03-15 |
| PH12014502330B1 (en) | 2015-01-12 |
| US9828686B2 (en) | 2017-11-28 |
| US20150090600A1 (en) | 2015-04-02 |
| JP6119053B2 (en) | 2017-04-26 |
| WO2013157639A1 (en) | 2013-10-24 |
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